Gas absorbent material



J 4, 1957 P. LEMAlGRE-VOREAUX 2,794,932

GS ABSORBENT MATERIAL Filed Jan. 9. 1952 United States Patent O GAS ABSORBENT MATERIAL Pierre Lemaigre-Voreaux, Paris, France, assigner to Societe Anonyme Pour les Applications de lElectricite et des Gaz Rares-Etablssements Claude-Pu & Silva, Paris, France Application January 9, 1952, Serial No. 265,643

Claims priority, application France January 12, 1951 6 Claims. (Cl. 313178) This invention relates to a gas absorbent material comprising essentially at least one metal Selected from the group consisting of tantalum and zirconium, the material being intended to be used in apparatus wherein use is made of electricity.

It is known that the above-mntioned metals absorb gases, other than rare gases, by processes which depend on the metal and on the gas, and which are generally a chemical combination or adissolution. At not too high temperatures, the rapidity of absorption increases with increasing temperature of the metal; when this temperature is too high, however, the metal may release all or part of the gases it has absorbed at lower temperatures.

Due to this property of absorbing gases, tantalum and zirconium are used as getters, i. e. for removing undesirable gases particularly in vacuum or gas filled electronic apparatus.

The fact that the absorbent material comprises essentially tantalum or zirconium means that in this material, absorption is eiected, at least for its greater part, by tantalum or zirconium. The absorbent material according to the invention may comprise, as a more or less important portion, substances other than tantalum and zirconium, which substances may be emissive or inert, conducting or insulating materials or other substances acting as getters, etc.

When zirconium coated with zirconium oxide is used, it must not be heated, during the normal operation of the apparatus in which it is used, up to, or above, a temperature so high that this oxide is noticeably absorbed by zirconium metal. This temperature is about 700 C.

One object of this invention is to provide gas absorbent material which may constitute parts of electric discharge apparatus from which discharges cannot start.

Another object of this invention is to provide gas absorbent material which cannot short-circuit live conducting parts.

Still another object of this invention is to provide a gas absorbent material comprising essentially a gas absorbent metal coated with a highly resistive ooating of an and-emissive substance, the coating being permeable to the gases to be absorbed.

The term and-emissive is applied here to any coating hindering the production of discharges from the surface it covers. The permeability of the coating may be substantial only in the conditions to which the Subjacent metal is subjected during the normal operation of the apparatus for which the absorbent material is used; the permeability may be due to interstices in the coating, to an intermediate dissolution of the gases in the and-emissive substance, to an equilibrium reaction of the gases with said substance and with the absorbent metal, or to other reasons.

In drawings, which illustrate embodiments of the invention,

Figure 1 is an elevational view of an electrode for an electric discharge apparatus.

Figure 2 is a plan view of the same electrode.

2,794,932 Patented June 4, 1957 Figure 3 is an elevafiomal view of another electrode for an electric discharge apparatus.

Figure 4 is a plan view of the electrode shown in elevation in Figure 3.

Figure 5 is a transverse section of a portion of another electrode for an electric discharge apparatus.

The electrode shown in Figures 1 and 2, has a coil 4, of molybdemum wire coated with emissive substances. This coil is secured to nickel leadin wires 1 and 6, by pinching its ends 2 and 5 in the hook-like ends of said leadin wires;

Two thin tantalum sheets 3 and 7, folded so as partly to enclose the coil 4, are welded to the leadin wires 6 and 1 respectively. Each one of these sheets 3, 7 has,

for example, a thickness of 0.1 mm., a width of 5 mm.

and a developed length of 15 mm. The tantalum is coated with an oxide layer obtained electrolytically by passing an electric current between the tantalum sheet, welded to its leadin wire 1 or 6 which sheet acts as an anode, and a tungsten cathode, these two electrodes being immersed in nitric acid of a low concentration. trolysis is carried out under a D. C. voltage of about volts. The value of the electrolysis current decreases as the oxide layer thickens; when this value is substantially zero, electrolyss is stopped. The oxide layer thus obtained, the thickness of which is of the order of one micron, is sufliciently thin to allow gases to pass through it and reach the subjacent tantalum metal where they are absorbed; it is suflicienfly thick to prevent the sheets 3 and 7 from acting as an anode or cathode when the electrode shown in Figs. 1 and 2 is mounted in an electric discharge apparatus. The sheets 3 and 7, during the operation of the electric discharge apparatus utilizing the electrode shown, are raised to a relatively low temperature; but as their surface is fairly large, they absorb, nevertheless, in a sufiicient manner the detrimental gases existing inside the electric discharge apparatus during the operation thereof. Said gases may have been left over as a result of a poor degassing of this apparatus, or may be released for instance by the electrodes.

The and-emissive oxide coating on the sheets 3 and 7 prevents them from acting as.electrodesg the anode and cathode glows remain therefore,, at each halfperiod of the current, when this current is alternating, localized in the vicinity of the coil 4, instead of passing from V the latter to the sheets, and vice versa; thus the luminous flicker of the ends of the lamp comprising such electrodes is decreased.

Another advantage of this and-emissive coating in the case of alternating current is that, since the sheets can no longer act as anodes, the coil 4 is heated by the entire heat evolved at the electrode by the anode and cathode voltage drops, which makes it possible to give it larger dimensions and, hence, to contain a larger store of emissive materials than if it were acting only as a cathode.

Still another dvantage is that this coating prevents the formation of acathode spot on one of these sheets; such a spot would locally heat the tantalum which, then, would release the gases it absorbed previously.

The above arrangement shown for the sheets enables them to intercept an important part of the particles emitted by ionic sputtering by the coil 4. If such an advantage is of little importance from the standpoint of a possible economy of tantalum, sheets with a smaller area may be used, or that sheet which is attached to the leadin wire not connected to the current source may even be omitted.

Figures 3 and 4 show, respectively, in elevation and in plan, au electrode comprising mainly a double Wound tungsten filament, 10, coated with emissive substances; the ends of this filament are welded to the leadin wires l, 6 of the electrode.

Here, the absorbent materia lis in the shape of two Electantalum wires,9 and 11, welded to the lead-in wires 1 and 6 and placed inside the large'r of the tWo cdils idwhich the tungsten filament is wound. This location allows the tantalurn to be heated, during the operation of the. discharge apparatus having the lectrode shown in Figures 3 and 4, to a temp er1ture at whih tantalm abs'orbs undesirable gases fairly rapidlyf Here again, the tantalum is coated with a layer of tantalum oxid' of the order of one micron by anodic oxidation, as in the fore'goingfexample.- This coating offersthe advantage, onlth orie 10 baud, of avoiding the short-circuiting of part of the wit id: ing 10 in case the latter, comes incontact with one of the wires 9 and 11, and on the otherhand, of prenting,. the discharge from starting from one of the.wires and hence heating the latter to the point where it givesgup tbe -Theelectrode shown comprises -two tantalum wires,- 9 and 11;in some cases, iftherejis little -gals tobelab;j sorbed, one wire only may be sufficiht.

Figure 5 shows, in section throughihe,plane passing,-

throughthe leadin Wires, 1 and 6, a portion of an.lectrodehaving a coiled coil filament, similarltd that showri. in Figures 3 and 4, but in which,the absorbent material is arrangeo difEerently. The tungsten filament 15, 0.08

mm. in diamcter,,for instance, is 'wound into a primary helix 13 with an inner diameter of 0.15 mm; for instance; this primary helix, a few turn of Which only are shown in Figure 5, is itself wound into a.secondary helix with an inner diameter of 0.7 mm., which is that shown atl0 on Figures 3 and 4. The emissive'coating 14 of the helix 13 comprises, at least in part aftr ,tieatment, barium oxide and small amounts of metallic barium; this emissive coating, in addition, in the present case, comprises tantalum grains 16 oxidized superficiall.

This oxidizing may be iected ither before the grains.

are mixed with the activating substance giving rise to the'emissive oxides', or during thetrmation of said oxides. It is,possible, for: instance, to operateas follows: First, -the double wound wire 15 is coated with a mixture of hydratedbaryta and -tantalum in nnc&xidized grains, 40

and anlectric current is passed throughIthe.filrmerit 15 so as to melt the baryta. Theri the electrode comprising this filament 15 is mbunted, together with a .similarlctrode,in the erivelope of the electric. discharge appaiatus in which it is desired to use these lctrodsithis assembly is then degassed byheating in vacuum, which dhydrates the bryta, andis thon Subsquently filld with a rare gas. Finally, a discharge is caused to.passbetween the clec-- trodes soas to activate thm, i. e. to reduce part of the baryta into metal barim. This activation b dischirges in a rare gas atmosphere may consist, forinstance,iifth support of the emissive layer is a coiled coi! tungsten fila ment 0.08 mm. in diameter, in a successionbf dischrges of 10 seconds each, separated by restperiods of 5 seconds,

this being crirried out for a half-hour; ea ch discharge is started without preheatingthelectrodes,- by using a sufiicient voltage, and offers a current value of 0.475 arnpere, Which is sligbtly higher than thcnormal current of 0.420 ampere of the dischrge in the electric dischaige apparatus in which the electrod being activated willb mounted. All these operations are known, for the manufacture of fluorescent lainpis -for instance;inthe present case, they have an additional effect: the tantalum grains are surface oxidized b the baryt, pairticularlyduririgthe activation of the electrods, which provides them with an anti-cmissive oxidc .coatifig. When using an activating substance other than barium hydrate, a suitabl treatment is employed.for surface iidizihgthe. tantlum or zirconium; this treatment niay, 'in'sonle cases, be similar to that required for the manufacture of the electrodefir- 7o ploying this other activating substance when..the emissive mixture does not contain either taritluni or zirconium, but adaptedso as to obtain the desired surface oxidizirg.

By way of example, an electrode designed for a lamp with a discharge current of 0.4 ampere, mav comprise 5 milligrams of barium oxide and 1 to 2 miIligrams of tantalum in grains of about 400 mesh. The oxide layer covering the metal grains oifers the advantage that these grains do not increase the conductivity of the emissive layer, as would be the case with bare metal grains.

In the above embodiments, tantalum only has bcen indicatcd as a gas absbrbing metal, this metal bcing, in general, easier to use thon zirconium. Zirconium, how ever, Which is only very slightly volatile and Which abserbe gases particularly well ata fairly high temperaiure, may also be used.

The absorbent material according to the present invention may also be used when the emissive matcrials are b o n; iv fin ubstan s p n b ri m compounds, for example from compounds of other alkalime earth metals, mixed or not with barium compounds or from thorium oxide.

Numerous other forms and applications of the absorbent material may be imagined Within the scope of the present invention.

The. tantalum or zirconium metal may, for instance, be coated with alumina or magnesia or other suitable electrically insulating substance,insteadef an oxide of the metal.

The present invention may also have applications othcr than to gasconselectric discharge apparatus. For instance, thetantalum or zirconium tapes or Wires uscd for improving the vacuum inside an enclosure, for example in a container whcre deposits are etected by evaporation in vacuum, may also be provided with an insulating coating; insuch a case, it is possible to place the tapes or wires in the immediate vicinity of or inside the tungsten heating-coil carrying the metal to be evaporated, said tapes or wires being placed in positions similar to that of the sheets 3, 7 or of the Wires 9, 11.

I claim:

1. A process for the manufacture of an electrode for gascons electric discharge lamp comprisng gas absorbefit material and at least one electrode, said electrode having a support and a coatingof electronemissive substance on the support, which comprises, providing particles of at least one metal selected from the group consisting of tantalum andzirconium with a coating of highiy resistive substance, this coating being permeable to the gases to be absorbed and bcing sufliciently thiokto resist the emission of electrons from the metal, mixing said coated particies with activating substances, coatingsaid support with said mixture, and subjecting said mixt ure to a heat treatment adapted to change activating substances to electroncmitting substances.

2.. A process for the manufacture of. an electrode for gaseos electric dischargelamp comprising gas absorberit material and at least one electrode, said electrode havinga supportand a coating of electron-emissive substance on the support, which comprises, mixing particles of atleast one met'aiselected from the group consisting of tantalum and zirconium with oxidizing activating substances, coating the support with said mixture, and subjecting said mixture to a heat treatment adapted to change said activating substances to electron emitting substances and to superficially oxidize said particles, said superficial oxide constituting a coating permeable to the gases tobe absorbed andsufficently thick to 1esist the omission of electrons from the metal.

3. A gascons electric discharge lamp having a sealcd envelope and comprising therein an electrodc and a gas absorbent materiai.or gtter, said electrode having a coating of electron-emissive substance, said materia] or getter comprising at least one metal selected from the group consistingof tantalum and zirconium and being in contact with the discharge atmosphere of said lump and being hea ted by the electrode of the lamp when the lamp is in operation, said material-or ge tter having a coating ofoxidq;ofi said metal whichconting is permeable to the gases to be absorbed and is of suflcent thickness to resist the emission of elect1ons from the metal constituting the gas absorbent mateal.

4. A discharge lamp as set forth in Claim 3, wherein the material takes the form of a thin sheet located in the vicinity of the electrode.

5. A discharge lamp as set forth in claim 3, wherein the electrode comprises a filament wound into a helix, and wherein the material is located inside the helix.

6. A disharge lamp as set forth in claim 3, wherein said gas absorbent material is mixed with said electron emissive substance.

References Cited in the file of this patent UNITED STATES PATENTS 1,787,672 Davenport Jan. 6, 1931 6 Boer May 17, Anderson Dec. 13, Kerk Feb. 28, De Boer et al. Sept. 5, De Boer et al. lune 26, Lederer Sept. 13, Wooten Jan. 23, Taylor Feb. 6, Rothstein Nov. 1, Ruscetta Sept. 4, 

